全文获取类型
收费全文 | 444篇 |
免费 | 27篇 |
专业分类
化学 | 358篇 |
晶体学 | 1篇 |
力学 | 3篇 |
数学 | 59篇 |
物理学 | 50篇 |
出版年
2023年 | 2篇 |
2022年 | 6篇 |
2021年 | 8篇 |
2020年 | 10篇 |
2019年 | 10篇 |
2018年 | 5篇 |
2017年 | 6篇 |
2016年 | 14篇 |
2015年 | 18篇 |
2014年 | 13篇 |
2013年 | 30篇 |
2012年 | 20篇 |
2011年 | 30篇 |
2010年 | 22篇 |
2009年 | 16篇 |
2008年 | 25篇 |
2007年 | 20篇 |
2006年 | 24篇 |
2005年 | 20篇 |
2004年 | 20篇 |
2003年 | 14篇 |
2002年 | 13篇 |
2001年 | 6篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 8篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 10篇 |
1991年 | 6篇 |
1990年 | 7篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 6篇 |
1974年 | 2篇 |
1944年 | 1篇 |
1932年 | 1篇 |
1924年 | 1篇 |
排序方式: 共有471条查询结果,搜索用时 46 毫秒
41.
42.
Susanne Schmidt Michaela Zietz Monika Schreiner Sascha Rohn Lothar W. Kroh Angelika Krumbein 《Rapid communications in mass spectrometry : RCM》2010,24(14):2009-2022
Kale is a member of the Brassicaceae family and has a complex profile of flavonoid glycosides. Therefore, kale is a suitable matrix to discuss in a comprehensive study the different fragmentation patterns of flavonoid glycosides. The wide variety of glycosylation and acylation patterns determines the health‐promoting effects of these glycosides. The aim of this study is to investigate the naturally occurring flavonoids in kale. A total of 71 flavonoid glycosides of quercetin, kaempferol and isorhamnetin were identified using a high‐performance liquid chromatography diode‐array detection/electrospray ionization multi‐stage mass spectrometry (HPLC‐DAD/ESI‐MSn) method. Of these 71 flavonol glycosides, 27 were non‐acylated, 30 were monoacylated and 14 were diacylated. Non‐acylated flavonol glycosides were present as mono‐, di‐, tri‐ and tetraglycosides. This is the first time that the occurrence of four different fragmentation patterns of non‐acylated flavonol triglycosides has been reported in one matrix simultaneously. In addition, 44 flavonol glycosides were acylated with p‐coumaric, caffeic, ferulic, hydroxyferulic or sinapic acid. While monoacylated glycosides existed as di‐, tri‐ and tetraglycosides, diacylated glycosides occurred as tetra‐ and pentaglycosides. To the best of our knowledge, 28 compounds in kale are reported here for the first time. These include three acylated isorhamnetin glycosides (isorhamnetin‐3‐O‐sinapoyl‐sophoroside‐7‐O‐D‐glucoside, isorhamnetin‐3‐O‐feruloyl‐sophoroside‐7‐O‐diglucoside and isorhamnetin‐3‐O‐disinapoyl‐triglucoside‐7‐O‐diglucoside) and seven non‐acylated isorhamnetin glycosides. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
43.
We have prepared an l-tyrosine derivative bearing a d-threo ketose moiety by a convenient chemoenzymatic route. This compound is of potential interest for developing stereospecific assays for enzymes catalyzing C-C bond cleavage such as transketolase. We showed in vitro by analytical studies (LC/MS and 31P NMR) that this compound can release l-tyrosine in the presence of wild type TK extract and bovine serum albumin. This assay is the first step towards a mutant TK selection test that could be developed for yeast cells auxotrophic for l-tyrosine. 相似文献
44.
45.
46.
Clemens Schwarzinger Angelika Pfeifer Harald Schmidt 《Monatshefte für Chemie / Chemical Monthly》2002,49(5):1-7
Analytical pyrolysis in combination with gas chromatography and mass spectrometry or a nitrogen-phosphorus detector, respectively, were used to characterize the quaternization reagent glycidyltrimethylammonium chloride and a cationic cotton fabric. Trimethylamine was shown to be the most abundant nitrogen-containing product in the pyrolysis of glycidyltrimethylammonium chloride and was thus used for the quantification of the nitrogen content of the cationic cotton fabric. The results were compared to those obtained by traditional methods such as Kjeldahl and elemental analysis. It could be shown that pyrolysis is well suited for monitoring the nitrogen content of cellulose fibers. 相似文献
47.
48.
Angelika Baranowska Krzysztof Z. Ła̧czkowski Andrzej J. Sadlej 《Journal of computational chemistry》2010,31(6):1176-1181
We have carried out extensive studies on the basis set dependence of the calculated specific optical rotation (OR) in molecules at the level of the time–dependent Hartree–Fock and density functional approximations. To reach the limits of the basis set saturation, we have devised an artificial model, the asymmetrically deformed (chiral) methane (CM) molecule. This small system permits to use basis sets which are prohibitively large for real chiral molecules and yet shows all the important features of the basis set dependence of the OR values. The convergence of the OR has been studied with n‐aug‐cc‐pVXZ basis sets of Dunning up to the 6–ζ. In a parallel series of calculations, we have used the recently developed large polarized (LPolX) basis sets. The relatively small LPolX sets have been shown to be competitive to very large n‐aug‐cc‐pVXZ basis sets. The conclusions reached in calculations of OR in CM concerning the usefulness of LPolX basis sets have been further tested on (S)‐methyloxirane and (S)‐fluoro‐oxirane. The smallest set of the LPolX family (LPol–ds) has been found to yield OR values of similar quality as those obtained with much larger Dunning's aug‐cc‐pVQZ basis set. These results have encouraged us to carry out the OR calculations with LPol–ds basis sets for systems as large as β‐pinene and trans‐pinane. In both cases, our calculations have lead to the correct sign of the OR value in these molecules. This makes the relatively small LPol–ds basis sets likely to be useful in OR calculations for large molecules. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
49.
Wolfgang Holzer Angelika Ebner Karin Schalle Gyselle Batezila Gernot A. Eller 《Journal of fluorine chemistry》2010,131(10):1013-1024
A straightforward, two-step synthesis of fluoro substituted chromeno[2,3-c]pyrazol- and [1]benzothieno[2′,3′:5,6]pyrano[2,3-c]pyrazol-4(1H)-ones, respectively, is presented. Hence, treatment of 1-substituted or 1,3-disubstituted 2-pyrazolin-5-ones with fluoro substituted 2-fluorobenzoyl chlorides or 3-chloro-6-fluoro-1-benzothiophene-2-carbonyl chloride using calcium hydroxide in refluxing 1,4-dioxane gave the corresponding 4-aroylpyrazol-5-ols, which were cyclized into the fused ring systems. 5-Fluorochromeno[2,3-c]pyrazol-4(1H)-one was obtained upon treatment of the 1-(4-methoxybenzyl) protected congener with trifluoroacetic acid. Treatment of 5-fluorochromeno[2,3-c]pyrazol-4(1H)-ones with methylhydrazine afforded novel tetracyclic ring systems such as 2-methyl-7-phenyl-2,7-dihydropyrazolo[4′,3′:5,6]pyrano[4,3,2-cd]indazole. Detailed NMR spectroscopic investigations (1H, 13C, 15N, 19F) with the obtained compounds were undertaken. 相似文献
50.